Integrated hydrothermal process to upgrade heavy oil

ABSTRACT

An integrated hydrothermal process for upgrading heavy oil includes the steps of mixing a heated water stream and a heated feed in a mixer to produce a mixed fluid, introducing the mixed stream to a reactor unit to produce a reactor effluent that includes light fractions, heavy fractions, and water, cooling the reactor effluent in a cooling device to produce a cooled fluid, depressurizing the cooled fluid in a depressurizing device to produce a depressurized fluid, introducing the depressurized fluid to a flash drum configured to separate the depressurized fluid into a light fraction stream and a heavy fraction stream. The light fraction stream includes the light fractions and water and the heavy fraction stream includes the heavy fractions and water. The process further includes the step of introducing the heavy fraction stream to an aqueous reforming unit that includes a catalyst to produce an aqueous reforming outlet.

RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 15/914,667 filed on Mar. 7, 2018, which is relatedand claims priority to U.S. Pat. App. No. 62/468,721 filed on Mar. 8,2017. For purposes of United States patent practice, this applicationincorporates the contents of the provisional application by reference inits entirety.

TECHNICAL FIELD

Disclosed are methods for upgrading petroleum. Specifically, disclosedare methods and systems for upgrading petroleum using an integratedhydrothermal process.

BACKGROUND

Supercritical water has many advantages when used to upgrade heavy oil.The extent of upgrading in supercritical water processes is limited bythe amount of hydrogen and the instability of catalysts in supercriticalwater.

The high temperature in the supercritical water reactor induces thermalcracking of chemical bonds such as carbon-sulfur bonds and carbon-carbonbonds. Broken bonds are filled with other atoms or by formingunsaturated bonds. Preferably the broken bonds are filled with hydrogento avoid intermolecular condensation and generation of olefins andaromatics. While olefins are valuable chemicals, low stability ofunsaturated bonds can degrade products by forming gums. Althoughhydrogen from the water molecule can participate in cracking reactions,the extent of hydrogen donation from water is limited in supercriticalwater condition due to high hydrogen-oxygen bond energy. Products from asupercritical water process can have higher aromaticity and olefinicitythan the feed petroleum, which has a negative effect on the economicvalue of the products.

The harsh conditions in a supercritical water process results inunstable catalysts. Disintegration of heterogeneous catalysts isfrequently observed in supercritical water. Homogeneous catalysts, suchas organometallic compounds, can be transformed to inactive form undersupercritical water condition. However, hydrogen abstraction from watercan be benefited from in the presence of catalyst in supercriticalwater.

SUMMARY

Disclosed are methods for upgrading petroleum. Specifically, disclosedare methods and systems for upgrading petroleum using an integratedhydrothermal process.

In a first aspect, an integrated hydrothermal process for upgradingheavy oil is provided. The integrated hydrothermal process includes thesteps of mixing a heated water stream and a heated feed in a mixer toproduce a mixed fluid, where the heated water stream is supercriticalwater and the heated feed is at a feedstock temperature less than 300degrees Celsius (deg C.) and a feedstock pressure greater than thecritical pressure of water, introducing the mixed stream to a reactorunit to produce a reactor effluent, allowing conversion reaction tooccur in the reactor unit is maintained at a temperature greater thanthe critical temperature of water and at a pressure greater than thecritical pressure of water, wherein the conversion reactions areoperable to upgrade the hydrocarbons in the mixed fluid such that thereactor effluent includes light fractions, heavy fractions, and water.The integrated hydrothermal process further including the steps ofcooling the reactor effluent in a cooling device to produce a cooledfluid at a temperature less than the critical temperature of water andless than the temperature of the reactor effluent, depressurizing thecooled fluid in a depressurizing device to produce a depressurized fluidat a pressure less than the steam pressure corresponding to thetemperature of the cooled fluid such that water in the depressurizedfluid is present as steam, introducing the depressurized fluid to aflash drum, separating the depressurized fluid in the flash drum toproduce a light fraction stream and a heavy fraction stream. The lightfraction stream includes the light fractions and water and the heavyfraction stream includes the heavy fractions and water, where the heavyfraction stream includes a water content between 0.1 percent by weight(wt %) and 10 wt %. The integrated hydrothermal process further includesintroducing the heavy fraction stream to an aqueous reforming unit, andallowing upgrading reactions to occur in the aqueous reforming unit toproduce an aqueous reforming outlet. The aqueous reforming unit includesa catalyst operable to catalyze upgrading reactions in the presence ofsteam. The aqueous reforming outlet includes a greater concentration oflight fraction relative the petroleum feed.

In further aspects, the integrated hydrothermal process includes thesteps of reducing the temperature of the light fraction stream in alights cooling device to produce a cooled light fraction at atemperature of 50 deg C., introducing the cooled light fraction to alights separation zone, separating the cooled light fraction in thelights separation zone to produce a gas product, a petroleum product,and a water product. In further aspects, the integrated hydrothermalprocess includes the steps of introducing the petroleum product to ahydrogenation unit to produce a hydrogenated product. In furtheraspects, the integrated hydrothermal process includes the steps ofseparating a slip stream from the gas product, introducing the slipstream to a gas sweetening unit, removing an amount of hydrogen sulfidefrom the slip stream to produce a sweetened gas stream, and introducingthe sweetened gas stream to the aqueous reforming unit. In furtheraspects, the integrated hydrothermal process includes the steps ofmixing the aqueous reforming outlet and the light fraction stream in aproduct mixer to produce a mixed fraction, reducing the temperature ofthe mixed fraction in a lights cooling device to produce a cooled mixedfraction at a temperature of 50 deg C., introducing the cooled mixedfraction to a lights separation zone; separating the cooled mixedfraction in the lights separation zone to produce a gas phase product, apetroleum phase product, and a water phase stream. In further aspects,the integrated hydrothermal process includes the steps of increasing apressure of a petroleum feed in a feed pump to produce a pressurizedfeed, where the pressure of the pressurized feed is greater than thecritical pressure of water, increasing a temperature of the pressurizedfeed in a feed heater to produce the heated feed at the feedstocktemperature, increasing a pressure of a water stream in a water pump tocreate a pressurized water at a pressure greater than the criticalpressure of water; and increasing a temperature of the pressurized waterin a water heater to produce the heated water stream, where the heatedwater is at a water temperature. In further aspects, the petroleum feedis selected from the group consisting of whole range crude oil, reducedcrude oil, atmospheric distillates, atmospheric residue streams, vacuumdistillates, vacuum residue streams, cracked product streams, such aslight cycle oil and coker gas, decanted oil, C10+ oil and other streamsfrom an ethylene plant, liquefied coal, and biomaterial-derivedhydrocarbons. In further aspects, the catalyst is selected from thegroup consisting of a homogeneous catalyst and a heterogeneous catalyst.In further aspects, the catalyst is a heterogeneous catalyst thatincludes an active species, a promoter, and a support material. Infurther aspects, the heterogeneous catalyst is a 2 wt % Ni-5 wt % Mgcatalyst supported on silicon dioxide. In further aspects, the catalystis a homogeneous catalyst that includes an active species and a ligand.In further aspects, the integrated hydrothermal process includes thesteps of dispersing the catalyst in a dispersal fluid to produce acatalyst feed, where dispersal of the catalyst in the dispersal fluid isachieved using ultrasonic waves; injecting the catalyst feed at aninjection rate into the flash drum such that the injection ratemaintains a weight ratio of hydrocarbons to catalyst in the rangebetween 0.05 and 0.07, such that the catalyst mixes with the heavyfraction to produce a heavy stream; and introducing the heavy stream tothe aqueous reforming unit. In further aspects, a ratio of a volumetricflow rate of water to a volumetric flow rate of a petroleum feed atstandard ambient temperature and pressure is between 1:10 and 10:1.

In a second aspect, an integrated hydrothermal system for upgradingheavy oil is provided. The integrated hydrothermal system includes amixer configured to mix a heated water stream and a heated feed toproduce a mixed fluid, where the heated water stream is supercriticalwater, where the heated feed is at a feedstock temperature less than 300deg C. and a pressure greater than the critical pressure of water, areactor unit fluidly connected to the mixer, the reactor unit configuredto maintain a temperature greater than the critical temperature ofwater, and further configured to maintain a pressure greater than thecritical pressure of water such that conversion reactions occur in thereactor unit, the conversion reactions are operable to upgrade thehydrocarbons in the mixed fluid such that a reactor effluent includeslight fractions, heavy fractions, and water, a cooling device fluidlyconnected to the reactor unit, the cooling device configured to reducethe temperature of the reactor effluent to produce a cooled fluid at atemperature greater than the critical temperature of water and less thanthe temperature of the reactor effluent, a depressurizing device fluidlyconnected to the cooling device, the depressurizing device configured toreduce the pressure of the cooled fluid to produce a depressurized fluidat a pressure less than the steam pressure corresponding to thetemperature of the cooled fluid such that water in the depressurizedfluid is present as steam, a flash drum fluidly connected to thedepressurizing device, the flash drum configured to separate thedepressurized fluid into a light fraction stream and a heavy fractionstream, where the light fraction stream includes the light fractions andwater, where the heavy fraction stream includes the heavy fractions andwater, where the heavy fraction stream includes a water content between0.1 wt % and 10 wt %, and an aqueous reforming unit fluidly connected tothe flash drum, the aqueous reforming unit configured to upgrade theheavy fraction stream to produce an aqueous reforming outlet. Theaqueous reforming unit includes a catalyst, where the catalyst isoperable to catalyze upgrading reactions in the presence of steam.

In other aspects, the integrated hydrothermal system further includes alights cooling device fluidly connected to the flash drum, the lightscooling device configured to reduce the temperature of the lightfraction stream to produce a cooled light fraction at a temperature of50 deg C., a lights separation zone, the lights separation zoneconfigured to separate the cooled light fraction into a gas product, apetroleum product, and a water product. In other aspects, the integratedhydrothermal system further includes a hydrogenation unit fluidlyconnected to the lights separation zone, the hydrogenation unitconfigured to produce a hydrogenated product. In other aspects, theintegrated hydrothermal system further includes a gas sweetening unitfluidly connected to the lights separation zone, the gas sweetening unitconfigured to remove a portion of hydrogen sulfide from a slip stream ofthe gas product to produce a sweetened gas stream. In other aspects, theintegrated hydrothermal system further includes a product mixer fluidlyconnected to the aqueous reforming unit, the product mixer configured tomix the aqueous reforming outlet and the light fraction stream toproduce a mixed fraction, a lights cooling device fluidly connected tothe product mixer, the lights cooling device configured to reduce thetemperature of the mixed fraction to produce a cooled mixed fraction ata temperature of 50 deg C., a gas-liquid separator fluidly connected tothe lights cooling device, the gas-liquid separator configured toseparate the cooled mixed fraction into a gas phase product and a liquidphase product, and an oil-water separator fluidly connected to thegas-liquid separator, the oil-water separator configured to produce apetroleum phase product and a water phase stream.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the scope willbecome better understood with regard to the following descriptions,claims, and accompanying drawings. It is to be noted, however, that thedrawings illustrate only several embodiments and are therefore not to beconsidered limiting of the scope as it can admit to other equallyeffective embodiments.

FIG. 1 provides a simplified process diagram of the process.

FIG. 2 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 3 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 3A provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 3B provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 4 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 4A provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 5 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 6 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 7 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 8 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 9 provides a process diagram of one embodiment of an integratedhydrothermal process.

FIG. 10 is a graphical representation of the distillation curves for thehydrocarbons in the reactor effluent, hydrocarbons in the light fractionstream, and hydrocarbons in the heavy fraction stream for Example 1.

FIG. 11 provides a process diagram of the process of Example 3.

DETAILED DESCRIPTION

While the scope will be described with several embodiments, it isunderstood that one of ordinary skill in the relevant art willappreciate that many examples, variations and alterations to theapparatus and methods described here are within the scope and spirit.Accordingly, the embodiments described are set forth without any loss ofgenerality, and without imposing limitations, on the embodiments. Thoseof skill in the art understand that the scope includes all possiblecombinations and uses of particular features described in thespecification.

Described here are processes and systems of an integrated hydrothermalprocess. An integrated hydrothermal process can combine a supercriticalwater process and a subcritical water process. Advantageously, theaddition of the subcritical water process provides an integrated systemthrough which the unconverted hydrocarbons from the supercritical waterprocess can be converted. An integrated hydrothermal process improvesenergy efficiency while minimizing complexity of the system.Advantageously, the milder conditions of the subcritical water processas compared to the supercritical water process allow a catalyst to beused in the subcritical water process.

As used throughout, “external supply of hydrogen” refers to hydrogen, ingas (H₂) or liquid form, supplied as a feed or part of a feed to a unitin the system. External supply of hydrogen does not encompass hydrogenpresent in the petroleum feedstock.

As used throughout, “external supply of catalyst” refers to a catalystadded to a unit as either a part of the feed to the unit or present inthe empty unit, for example as a catalyst bed. External supply ofcatalyst does not encompass compounds that could have a catalytic effectand are part of the petroleum feedstock or produced through reactionswithin the units of the system.

As used throughout, “in the absence of” means does not contain, does notinclude, does not comprise, is without, or does not occur.

As used throughout, “heavy fraction” refers to the fraction in ahydrocarbon fluid having a True Boiling Point 10 percent (TBP 10%) thatis greater than 650 degrees Fahrenheit (deg F.) (343 deg C.), andalternately greater than 1050 deg F. (566 deg C.). The heavy fractioncan include components from a petroleum feed that were not converted inthe supercritical water reactor. The heavy fraction can also includehydrocarbons that were dimerized or oligomerized in the supercriticalwater reactor.

As used throughout, “light fraction” refers to the fraction that remainsof a hydrocarbon fluid after the heavy fraction is removed. TBP 90% ofthe light fraction is less than 650 deg F. and alternately less than1050 deg F.

The boiling point ranges of the light fraction and the heavy fractioncan depend on the target properties of the products, such as theconcentration of unsaturated hydrocarbons in the product or theviscosity. For example, if the light fraction can be a valuable producteven when it contains amounts of unsaturated hydrocarbons, then theheavy fraction can have a TBP 10% greater than 1050 deg F. so as toreduce the load on the aqueous reforming unit. For example, if the lightfraction is to be used as a low viscosity fuel oil, the heavy fractioncan have a TBP 10% greater than 650 deg F.

As used throughout, “trim” refers to the adjustment of temperature of afluid within a vessel by an amount in the range from 10% less to 10%greater than the temperature of the fluid. By way of an example, a fluidat 450 deg C. can be trimmed to 410 deg C.

As used throughout, “homogeneous catalyst” refers to catalysts which aredissolved in fluid at ambient conditions. Homogeneous catalysts canchange their solubility in a fluid by decomposition which can givecatalytic activity to the catalyst.

As used throughout, “sweeten” or sweetening” refers to the removal of aportion of hydrogen sulfide from a gas stream.

As used throughout, “coke” refers to the toluene insoluble materialpresent in petroleum.

As used throughout, “maltene phase” or “maltene fraction” refers to then-heptane solution fraction of hydrocarbons.

As used throughout, “upgrade” means to increase the API gravity,decrease the amount of impurities, such as sulfur, nitrogen, and metals,decrease the amount of asphaltene and increase the amount of the lightfraction.

It is known in the art that hydrocarbon reactions in supercritical waterupgrade heavy oil to produce products that have lighter fractions.Supercritical water has unique properties making it suitable for use asa petroleum reaction medium where the reaction objectives includeupgrading reactions, desulfurization reactions and demetallizationreactions, where supercritical water acts as both a hydrogen source anda solvent (diluent). Supercritical water is water greater than thecritical temperature of water and greater than the critical pressure ofwater. The critical temperature of water is 373.946 deg C. The criticalpressure of water is 22.06 megapascals (MPa). Without being bound to aparticular theory, it is understood that the basic reaction mechanism ofsupercritical water mediated petroleum processes is the same as aradical reaction mechanism. Thermal energy creates radicals throughchemical bond breakage. Supercritical water, acting as a diluent,creates a “cage effect” by surrounding radicals. The radicals surroundedby water molecules cannot react easily with each other, and thus,intermolecular reactions that contribute to coke formation aresuppressed. The cage effect suppresses coke formation by limitinginter-radical reactions compared to conventional thermal crackingprocesses, such as delayed coker. Hydrogen from the water molecules canbe transferred to the hydrocarbons through direct transfer or throughindirect transfer, such as the water gas shift reaction. While,supercritical water facilitates hydrogen transfer between molecules, itis inevitable to produce unsaturated hydrocarbons due to the limitedamount of available hydrogen. Unsaturated carbon-carbon bonds can bedistributed through the whole range of boiling points. Olefins, as arepresentative unsaturated hydrocarbon, are valuable chemicals, but lowstability can cause many problems such as gum formation when exposed toair. Thus, it is common practice in modern refinery to saturate olefinswith hydrogen in the presence of catalyst. Thermal cracking of aparaffin feed can produce paraffins and olefins having reduced numbersof carbons compared to the paraffin feed. The relative amount ofparaffins and olefins and the distribution of carbon numbers stronglydepends on the phase where the thermal cracking occurs. In the liquidphase, faster hydrogen transfer between molecules occurs due to the highdensity creating closer distances between the molecules which makeshydrogen transfer between molecules easier and faster. In the gas phase,methane, ethane, and other light paraffin gases are produced andconsumer large amounts of hydrogen. Thus, the liquid phase facilitatesthe formation of more paraffins in the liquid phase product as comparedto gas-phase cracking. Additionally, liquid phase cracking showsgenerally even distribution of the carbon numbers of the product whilegas phase cracking has more light paraffins and olefins in the product.

Referring to FIG. 1, a general process flow diagram of the process forconversion of heavy oil is provided. Stream A includes a mix ofpetroleum and water. Stream A is fed to a supercritical water process,such as a supercritical water reactor, where conversion reactions occurat or greater than the supercritical conditions of water. The productfrom the supercritical water reactor, Stream B, includes a lightfraction, a heavy fraction, and water. Stream B is introduced to a flashdrum at a pressure less than the pressure in the supercritical waterreactor. The flash drum produces Stream C and Stream D. Stream Dcontains the light fraction and water. Stream D can be subjected tofurther treatments, such as an alkali treatment as described in U.S.Pat. No. 9,005,432. The hydrocarbons in the light fraction can beconsidered upgraded and can be in the absence of further treatmentprocesses.

Stream C is a mixture of the heavy fraction and water from Stream B.Stream C is introduced to a subcritical water process, such as anaqueous reforming unit. The integrated hydrothermal process isadvantageous because the amount of water used in the supercritical waterprocess can be used in the subcritical water process. In the aqueousreforming unit, steam reforming occurs in the presence of a catalyst.The steam reforming reaction generates hydrogen, which is transferred tothe hydrocarbons that are contained in the heavy fraction. Upgradingreactions can occur in the aqueous reforming unit. The integratedhydrothermal process creates a treated feed for the aqueous reformingunit from the supercritical water reactor. The heavy fraction from thesupercritical water reactor can contain a high amount of unsaturatedbonds due to the breaking of bonds. Advantageously, the high amount ofunsaturated bonds enables the heat of the hydrogenation reaction in theaqueous reforming unit to maintain the temperature in the aqueousreforming unit. In contrast, when an untreated feed is fed to an aqueousreforming unit bond breaking occurs before the unsaturated compounds arehydrogenated from hydrogen. It is understood that “unstable” bonds, suchas in olefins, are preferred in an aqueous reforming unit, with hydrogengeneration and hydrogenation reactions.

Stream E contains upgraded hydrocarbons relative to Stream C. The orderof processing, supercritical water reactor and then an aqueous reformingunit, is the order necessary for producing Stream E. Supercritical watercan crack the heavy molecules in the absence of forming coke due to thecage effect. An aqueous reforming unit generates hydrogen andhydrogenation of unsaturated bonds. In the order of the integratedhydrothermal process, the supercritical water reactor cracks heavymolecules and the aqueous reforming unit hydrogenates the unsaturatedbonds on the cracked molecules, producing a product with lighterunsaturated bonds. In a reversed process, where aqueous reforming occursupstream of a supercritical water reactor, the final product wouldcontain a greater fraction of unsaturated bonds. Asphalthene isconcentrated in the heaviest fractions of crude oil, such as vacuumresidue. The specific gravity of vacuum residue is higher than water atnormal conditions, which means that the asphalthene fraction can settlein the water. Likewise, in a steam environment, the heavy fraction tendsto precipitate by gravity force unless intensive mixing occurs. Thus, inan aqueous reforming reactor, asphalthene can settle away from the steamcausing solid coke formation. Formation of solid coke means reducedliquid and gas yields. Supercritical water can have a high solubilitytoward hydrocarbons. Additionally, supercritical water is believed toswell aggregates of hydrocarbons, such as asphalthene. Advantageously,in the integrated hydrothermal process, some of the asphalthene can stayin the swollen state, which is beneficial to the aqueous reformingreactor. Advantageously, the supercritical water reactor can supplyenergy to the reactor effluent which can be carried through to the heavyfraction stream and can provide the energy for the aqueous reformingunit. Advantageously, the operating conditions in the aqueous reformingunit suppress the formation of coke.

Advantageously, aqueous reforming utilizes optimized process severities,the intensity of which can be measured by the P-value of the oil.P-value is a titrative technique that measures oil's asphaltenestendency to precipitate. Precipitation of the asphaltenes is the firststep in coking reactions. The P-value has a direct relation toasphaltenes content as well as paraffin content of the oil. Oil withgreater amounts of asphaltenes, but less paraffin content is more stablethan oil with less asphaltenes content, but greater amounts ofparaffins. For example, the P-values of Arabian light atmosphericresidue is 0.85 and for vacuum residue is 2.9. The minimum P-value foroil stability is 1.15. As oil is subjected to cracking, the P-value ofthe oil is reduced due to the generation of additional paraffins,paraffins tend to reduce the solvation power of oil towards asphaltenes.In at least one embodiment, the P-value of the petroleum feed is in therange of 1.3 and 3.5.

Referring to FIG. 2, an integrated hydrothermal process for theconversion of heavy oil is provided and described with reference to anintegrated hydrothermal system. Petroleum feed 115 is transferred tofeed heater 20 through feed pump 15. Pressurized feed 120 can be anysource of petroleum-based hydrocarbons, including heavy oil. Examples ofpetroleum-based hydrocarbon sources include whole range crude oil,reduced crude oil, atmospheric distillates, atmospheric residue streams,vacuum distillates, vacuum residue streams, cracked product streams,such as light cycle oil and coker gas, decanted oil, oil containinghydrocarbons with 10 or more carbons (C10+ oil) and other streams froman ethylene plant, liquefied coal, and biomaterial-derived hydrocarbons.The petroleum-based hydrocarbon source can be an individual stream froma refinery and combined streams from a refinery. The petroleum-basedhydrocarbon source can come from an upstream operation, such as aproduced oil stream. An example of a bio-derived material includes biofuel oil. In at least one embodiment, petroleum feed 115 is whole rangecrude oil. In at least one embodiment, petroleum feed 115 is anatmospheric residue stream. In at least one embodiment, petroleum feed115 is a vacuum residue stream. Atmospheric residue and vacuum residuestreams are bottom streams or bottom fractions from an atmosphericdistillation process or vacuum distillation process.

Feed pump 15 increases the pressure of petroleum feed 115 to producepressurized feed 120. Feed pump 15 can be any type of pump capable ofincreasing the pressure of petroleum feed 115. Examples of feed pump 15include a diaphragm metering pump. Pressurized feed 120 has a feedstockpressure. The feedstock pressure of pressurized feed 120 is at apressure greater than the critical pressure of water, alternatelygreater than about 23 MPa, and alternately between about 23 MPa andabout 30 MPa. In at least one embodiment, the feedstock pressure isabout 24 MPa.

Feed heater 20 increases the temperature of pressurized feed 120 toproduce heated feed 125. Feed heater 20 can be any type of heatingdevice that can increase the temperature of pressurized feed 120.Examples of feed heater 20 can include a gas-fired heater and a heatexchanger. Feed heater 20 heats pressurized feed 120 to a feedstocktemperature. The feedstock temperature of heated feed 125 is attemperature equal to or less than 350 deg C., alternately a temperatureless than 300 deg C., alternately a temperature between about 30 deg C.and 300 deg C., alternately a temperature less than 150 deg C.,alternately a temperature between 30 deg C. and 150 deg C., andalternately a temperature between 50 deg C. and 150 deg C. In at leastone embodiment, the feedstock temperature is 150 deg C. Keeping thetemperature of heated feed 125 less than 350 deg C. reduces, and in somecases eliminates the production of coke in the step of heating thefeedstock upstream of the reactor. In at least one embodiment,maintaining the feedstock temperature of heated feed 125 at or less thanabout 150 deg C. eliminates the production of coke in heated feed 125.Additionally, heating a petroleum-based hydrocarbon stream to 350 degC., while possible, requires heavy heating equipment, whereas heating to150 deg C. can be accomplished using steam in a heat exchanger. Heatingpressurized feed 120 to produce heated feed 125 prevents the formationof hot spots in the reactor that would be due to the reactor having torapidly heat mixed fluid 130, as the temperature of heated feed 125contributes to and maintains at a higher temperature, the temperature ofmixed fluid 130.

Water stream 100 is fed to water pump 5 to create pressurized water 105.In at least one embodiment, water stream 100 is demineralized water witha conductivity less than 1.0 micro Siemens per centimeter (μS/cm²) andalternately a conductivity less than 0.1 μS/cm². Water pump 5 can be anytype of pump capable of increasing the pressure of water feed 100.Examples of pumps suitable for use as water pump 4 include a diaphragmmetering pump. Pressurized water 105 has a water pressure. The waterpressure of pressurized water 105 is a pressure greater than thecritical pressure of water, alternately a pressure greater than about 23MPa, and alternately a pressure between about 23 MPa and about 30 MPa.In at least one embodiment, the water pressure is about 24 MPa.Pressurized water 105 is fed to water heater 10 to create heated waterstream 110.

Water heater 10 heats pressurized water 105 to a water temperature toproduce heated water stream 110. Water heater 10 can be any type ofheating device that can increase the temperature of pressurized water105. Examples of water heater 10 can include a gas-fired heater, and aheat exchanger. The water temperature of pressurized water 105 is atemperature greater than the critical temperature of water, alternatelya temperature greater than 380 deg C., alternately a temperature betweenabout 374 deg C. and about 600 deg C., alternately between about 374 degC. and about 450 deg C., and alternately greater than about 450 deg C.Heated water stream 110 is supercritical water. The upper limit of thewater temperature is constrained by the rating of the physical aspectsof the process, such as pipes, flanges, and other connection pieces. Forexample, for 316 stainless steel, the maximum temperature at highpressure is recommended to be 649 deg C. Temperatures less than 600 degC. are practical within the physical constraints of the pipelines. In atleast one embodiment, heated water stream 110 is greater than 380 deg C.Heated water stream 110 is supercritical water at conditions greaterthan the critical temperature of water and critical pressure of water.

Water stream 100 and petroleum feed 115 are pressurized and heatedseparately. In at least one embodiment, the temperature differencebetween heated feed 125 and heated water stream 110 is greater than 300deg C. Without being bound to a particular theory, a temperaturedifference between heated feed 125 and heated water stream 110 ofgreater than 300 deg C. is believed to increase the mixing of thepetroleum-based hydrocarbons present in heated feed 125 with thesupercritical water in heated water stream 110 in mixer 30. Heated waterstream 110 is in the absence of an oxidizing agent. Regardless of theorder of mixing, petroleum feedstock 115 is not heated greater than 350deg C. until after having been mixed with water stream 110 to avoid theproduction of coke.

Heated water stream 110 and heated feed 125 are fed to mixer 30 toproduce mixed fluid 130. Mixer 30 can include any mixer capable ofmixing a petroleum-based hydrocarbon stream and a supercritical waterstream. Examples of mixers for mixer 30 include static mixers, teefittings, ultrasonic mixers, and capillary mixers. Without being boundto a particular theory, supercritical water and hydrocarbons do notinstantaneously mix on contact, but require sustained mixing before awell-mixed or thoroughly mixed stream can be developed. A well-mixedstream facilitates the cage-effect of the supercritical water on thehydrocarbons. Mixed fluid 130 is introduced to reactor unit 40. Theratio of the volumetric flow rates of petroleum feed to water enteringreactor unit 40 at standard ambient temperature and pressure (SATP) isbetween about 1:10 and about 10:1, and alternately between about 1:5 and5:1. In at least one embodiment, the ratio of the volumetric flow rateof water to the volumetric flow rate of petroleum feedstock enteringreactor unit 40 is in the range of 1:1 to 5:1.

Having a well-mixed mixed fluid 130 can increase the conversion ofhydrocarbons in the reactor. The temperature of mixed fluid 130 dependson the water temperature of heated water stream 110, the feedstocktemperature of heated feed 125, and the ratio of heated water stream 110to heated feed 125. The temperature of mixed fluid 130 can be between270 deg C. and 500 deg C., alternately between 300 deg C. and 500 degC., and alternately between 300 deg C. and 374 deg C. In at least oneembodiment, the temperature of mixed fluid 130 is greater than 300 degC. The pressure of mixed fluid 130 depends on the water pressure ofheated water stream 110 and the feedstock pressure of heated feed 125.The pressure of mixed fluid 130 can be greater than 22 MPa.

Mixed fluid 130 is introduced to reactor unit 40 to produce reactoreffluent 140. In at least one embodiment, mixed stream 130 passes frommixer 30 to reactor unit 40 in the absence of an additional heatingstep. In at least embodiment, mixed stream 130 passes from mixer 30 toreactor unit 40 in the absence of an additional heating step, butthrough piping with thermal insulation to maintain the temperature.

Reactor unit 40 is operated at a temperature greater than the criticaltemperature of water, alternately between about 374 deg C. and about 500deg C., alternately between about 380 deg C. and about 480 deg C.,alternately between about 390 deg C. and about 450 deg C., alternatelybetween about 400 deg C. and about 500 deg C., alternately between about400 deg C. and about 430 deg C., and alternately between 420 deg C. andabout 450 deg C. In at least one embodiment, the temperature in reactorunit 40 is between 400 deg C. and about 460 deg C. Reactor unit 40 is ata pressure greater than the critical pressure of water, alternatelygreater than about 22 MPa, alternately between about 23 MPa and 35 MPa,and alternately between about 24 MPa and about 30 MPa. The residencetime of mixed fluid 130 in reactor unit 40 is greater than about 10seconds, alternately between about 10 seconds and about 5 minutes,alternately between about 10 seconds and 10 minutes, alternately betweenabout 1 minute and about 6 hours, and alternately between about 10minutes and 2 hours. Conversion reactions can occur in reactor unit 40.Exemplary conversion reactions include cracking, isomerization,alkylation, dimerization, aromatization, cyclization, desulfurization,denitrogenation, demetallization, and combinations thereof. Reactoreffluent 140 can include heavy fractions, light fractions, and water.

Reactor effluent 140 is fed to cooling device 50 to produce cooled fluid150. Cooling device 50 can be any device capable of reducing thetemperature of reactor effluent 140. In at least one embodiment, coolingdevice 50 is a heat exchanger. Cooled fluid 150 is at a temperature ator greater than the critical temperature of water. In at least oneembodiment, cooled fluid 150 is at a temperature less than the criticaltemperature of water. In at least one embodiment, the process forupgrading petroleum is in the absence of cooling device 50. Coolingdevice 50 can be designed to trim the fluid temperature. The temperatureof cooling device 50 facilitates flashing of depressurized fluid 155 inflash drum 60 without the need for further heating.

Cooled fluid 150 passes through depressurizing device 55 to producedepressurized fluid 155. Depressurizing device 55 can be any pressureregulating device capable of reducing fluid pressure. Examples ofpressure regulating devices that can be used as depressurizing device 55include pressure control valves, capillary elements, and back pressureregulators. In at least one embodiment, depressurizing device 55 can bea back pressure regulator. Depressurizing device 55 reduces the pressureof cooled fluid 150 to a pressure less than the steam pressure for thetemperature of depressurized fluid 155. As an example, at a temperatureof 350 deg C., steam is produced at a pressure less than 16.259 MPa; asa result, the pressure of depressurized fluid 155 should be less than16.259 MPa at 350 deg C. The amount of hydrogen in depressurized fluid155 is less than 1 wt % of the hydrocarbons in depressurized fluid 155.

In at least one embodiment, the process is in the absence of coolingdevice 50 and depressurizing device 55 is designed in consideration of areduction in temperature due to expansion of the fluid throughdepressurizing device 55.

For clarity, the water in the integrated hydrothermal system is liquidfrom the water pump to the water heater, the water in the system is atsupercritical conditions from the water heater to the depressurizingdevice, and is steam from the depressurizing device to the flash drum.

Depressurized fluid 155 is fed to flash drum 60. Flash drum 60 separatesdepressurized fluid 155 into light fraction stream 160 and heavyfraction stream 162. Flash drum 60 can be a simple fractionator, such asa flash drum. Advantageously, the temperature and pressure ofdepressurized fluid 155 are such that a flash drum can be used toseparate depressurized fluid 155 into the light fractions and the heavyfractions. Flash drum 60 can be designed to generate vapor inside. Lightfraction stream 160 includes light fractions and water. Heavy fractionstream 162 includes heavy fractions and water. The composition,including the petroleum composition and the amount of water, of each oflight fraction stream 160 and heavy fraction stream 162 depends on thetemperature and pressure in flash drum 60. The temperature and pressureof flash drum 60 can be adjusted to achieve the desired separationbetween light fraction stream 160 and heavy fraction stream 162. In atleast one embodiment, the temperature and pressure of flash drum 60 canbe controlled to achieve a water content in heavy fraction stream 162 ofgreater than 0.1 percent by weight (wt %), alternately between 0.1 wt %and 10 wt %, alternately between 0.1 wt % and 1 wt %, and alternatelybetween 1 wt % and 6 wt %. The unconverted fractions from petroleum feed115 are in heavy fraction stream 162. Flash drum 60 can include anexternal heating element (not shown) to increase the temperature of theinternal fluid. The external heating element can be any type known inthe art capable of maintaining or increasing the temperature in avessel. Flash drum 60 can include an internal heating element (notshown) to increase the temperature of the internal fluid. Flash drum 60can include an internal mixing device. The internal mixing device can byany type of internal mixing device known in the art capable of enhancingmixing of the internal fluid. In one embodiment, the internal mixingdevice is an agitator.

In an alternate embodiment, as shown with reference to FIG. 3,depressurized fluid 155 can be fed to phase separator 62 and separatedinto gas stream 362, oil stream 360, and spent water stream 364. Oilstream 360 can be fed to flash drum 60 to be separated into light stream366 and heavy fraction stream 162. Spent water stream 364 can be treatedand fed to the aqueous reforming unit. Treatment of spent water 364 caninclude filtering steps and deionizing steps. Light stream 366 can betreated as described with reference to light fraction stream 160 andFIG. 2. The embodiment of FIG. 3, combining phase separator 62 and flashdrum 60 can be used when the total dissolved solids in the waterfraction exiting reactor unit 40 is greater than 100 parts-per-millionby weight (wt ppm). A total dissolved solids of greater than 100 wt ppmcan contaminate the heavy fraction from the flash drum in the absence ofa three-phase oil water separator to separate the water with dissolvedsolids. In at least one embodiment, high total dissolved solids in thewater fraction exiting reactor unit 40 can be present when the petroleumfeedstock contains high inorganic content, such as a salt content higherthan 3.4 pounds per thousand, or a nickel and vanadium content higherthan 66 wt ppm.

Returning to FIG. 2, light fraction stream 160 is fed to lights coolingdevice 65 to produce cooled light fraction 165. Lights cooling device 65can be any type of heat exchanger capable of reducing the temperature oflight fraction stream 160. Examples of heat exchangers useful as lightscooling device 65 include shell and tube heat exchanger. The temperatureof cooled light fraction 165 can be at or less than 100 deg C.,alternately at or less than 75 deg C., and alternately at or less than50 deg C. In at least one embodiment, the temperature of cooled lightfraction 165 is at 50 deg C. In at least one embodiment, light fractionstream 160 can be fed through a pressure regulator. In at least oneembodiment, the pressure regulator can reduce the pressure of lightfraction stream 160 to ambient pressure.

Cooled light fraction 165 can be introduced to lights separation zone85. Lights separation zone 85 separates cooled light fraction 165 intogas product 180, petroleum product 190, and water product 192. Lightsseparation zone 85 can include multiple separation units in series orcan include a single three-phase separator. In at least one embodiment,as described with reference to FIG. 3A, lights separation zone 85includes a gas-liquid separator and an oil-water separator. Cooled lightfraction 165 can be introduced to gas-liquid separator 80 whichseparates cooled light fraction 165 into gas product 180 and liquidproduct 182. Liquid product 182 can be introduced to oil-water separator90 which separates liquid product 182 into petroleum product 190 andwater product 192. In at least one embodiment, as described withreference to FIG. 3B, lights separation zone 85 can include athree-phase separator. Cooled light fraction 165 can be introduced tothree-phase separator 84. Three-phase separator 84 can be any type ofseparation unit capable of separating a stream into a gas phasecomponent, a water component, and an oil component. Three-phaseseparator 84 separates cooled light fraction 165 to produce gas product180, petroleum product 190, and water product 192.

Returning to FIG. 2, the operating conditions in lights separation zone85 can be designed to target a composition in petroleum product 190. Thetemperature in lights separation zone 85 can be less than 100 deg C. Thepressure in lights separation zone 85 can be less than 5 MPa. In atleast one embodiment, the temperature in lights separation zone 85 canbe 50 deg C. In at least one embodiment, the pressure in lightsseparation zone 85 can be 0.2 MPa. Gas product 180 can includehydrocarbons present as gases, such as methane and ethane, and caninclude inorganic gases such as carbon monoxide, carbon dioxide,hydrogen sulfide, and hydrogen. Gas product 180 can be released toatmosphere, further processed, or collected for storage or disposal.Water product 192 can be recycled for use as water stream 100, can befurther processed, such as in a demineralization process, to remove anyimpurities and then recycled for use as water stream 100, or can becollected for storage or disposal. Petroleum product 190 can includeconverted hydrocarbons, such as olefins and aromatics. Petroleum product190 can include naphtha (hydrocarbons with an final boiling point (FBP)of 204 deg C.), distillates (hydrocarbons with a boiling point range of204 deg C. to 455 deg C.), vacuum gas oil (VGO) (hydrocarbons with aboiling point range of 455 to 540 deg C.), and unconverted oil(hydrocarbons with a boiling point range of greater than 540 deg C.). Inat least one embodiment, the hydrocarbons in petroleum product 190 arelighter, such that the hydrocarbons contain fewer carbon atoms, than thehydrocarbons in petroleum feed 115 and aqueous reforming outlet 170. Inat least one embodiment, petroleum product 190 can have improved APIgravity, viscosity reduction, and reduced sulfur as compared topetroleum feed 115.

Heavy fraction stream 162 is introduced to aqueous reforming unit 70 toproduce aqueous reforming outlet 170. Aqueous reforming unit 70 is asteam reforming unit. The operating conditions in aqueous reforming unit70 are such that water is present as steam. Aqueous reforming unit 70 isin the absence of liquid water.

Aqueous reforming unit 70 includes one or more reactors. Examples ofreactors that can be used as an aqueous reforming unit include vesseltype reactors, tubular type reactors, and combinations of vessel typeand tubular type reactors. Vessel type reactors can include an internalmixing device, such as an agitator. Tubular type reactors can have aratio of length to inner diameter of greater than 10, alternatelygreater than 30. Advantageously, introducing heavy fraction stream 162to aqueous reforming unit 70 in the absence of light fraction stream 160reduces the size of aqueous reforming unit 70, avoids introducingolefins to aqueous reforming unit 70 because the olefins are in lightfraction stream 160, and provides added stability to aqueous reformingunit 70 because asphaltenes are more stable in the absence of the lightfraction.

The temperature in aqueous reforming unit 70 is greater than 300 deg C.,alternately greater than 350 deg C., and alternately between 350 deg C.and 460 deg C. In at least one embodiment, the temperature in aqueousreforming unit 70 is 435 deg C. The pressure in aqueous reforming unit70 is between atmospheric pressure and the water saturation pressure atthe temperature such that the water is present as steam or superheatedsteam. For example, when the temperature in aqueous reforming unit 70 is435 deg C. the pressure is greater than atmospheric pressure and lessthan the critical pressure of water. The residence time of the internalfluid in aqueous reforming unit 70 is at least 8 minutes, andalternately at least 12 minutes. In at least one embodiment, theresidence time in aqueous reforming unit 70 is at least 12 minutes.Aqueous reforming outlet 170 contains a greater concentration of thelight fraction relative to petroleum feed 115. Aqueous reforming outlet170 is less viscous relative to petroleum feed 115. In at least oneembodiment, due to detachment of alkyl appendages and partial conversionof the maltene phase, the amount of asphaltene in aqueous reformingoutlet 170 is greater than in petroleum feed 115.

Aqueous reforming unit 70 combines the effects of temperature, pressure,residence time and catalyst. In aqueous reforming unit 70, upgradingreactions can occur in the presence of a catalyst. In at least oneembodiment, hydrogen can be generated in aqueous reforming unit 70. Inat least one embodiment, aqueous reforming unit 70 is in the absence ofan external supply of hydrogen. In aqueous reforming unit 70, hydrogencan be generated and upgrading reactions can occur in the presence ofcatalyst. Examples of upgrading reactions include reforming reactions,saturation reactions, hydrocarbon cracking reactions, dehydrocyclizationreactions, suppressing condensation reactions, demetallizationreactions, mono-aromatization reactions, and combinations of the same.The following reforming reactions can occur in aqueous reforming unit 70C_(n)H_(2n+2)+H₂O⇄CO+3H₂  reaction 1C_(n)H_(2n+1)OH+H₂O⇄CO+3H₂  reaction 2

Saturation reactions can include hydrogenation reactions. In at leastone embodiment, the catalyst in aqueous reforming unit 70 can catalyzethe upgrading reactions. Advantageously, reforming reactions are favoredby high temperatures.

The catalyst in aqueous reforming unit 70 does not deactivate in thepresence of steam. The catalyst can be a heterogeneous catalyst or ahomogeneous catalyst. In at least one embodiment, the catalyst is in theabsence of a combination of heterogeneous catalyst and homogeneouscatalyst, because in combination a homogeneous catalyst can plug orpoison a heterogeneous catalyst.

Heterogeneous catalysts can include active species, promoters, supportmaterials, and combinations of the same. Examples of active speciesinclude active species selected from group VII and group VIII transitionmetals, alkaline metals, alkaline earth metals, and combinations of thesame. In at least one embodiment, the catalyst is in the absence ofgroup IV transition metals. Examples of promoters can include promotersselected from boron and phosphorous. Examples of support materials caninclude support materials selected from alumina, silica, titania,zirconia, activated carbon, carbon black, and metal oxides. Theheterogeneous catalyst arrangement can include a fixed bed, a tricklebed, a honeycomb type, and a slurry bed. For a fixed bed or a tricklebed arrangement, the catalyst is in the form of an extrudate having asize that is less than one-tenth of the reactor inner diameter and a beddensity that maintains a pressure drop through the bed that is less than10% of the operating pressure of aqueous reforming unit 70. For ahoneycomb type arrangement, the active species are doped on a ceramichoneycomb, such as an alumina and silica-based ceramic, or a metalhoneycomb, such as stainless steel or high nickel alloy metal, where theopening on the honeycomb is sized to maintain a pressure drop throughthe bed that is less than 10% of the operating pressure of aqueousreforming unit 70.

In at least one embodiment, the heterogeneous catalyst can be introducedin a slurry bed arrangement by mixing the heterogeneous catalyst with adispersal fluid to produce a catalyst feed. In at least one embodiment,the catalyst can be a dissolved homogeneous catalyst that can act as akind of precursor for active catalyst particles. In at least oneembodiment, the dissolved homogeneous catalyst can change to oxide oranother solid compound when being subjected to a high temperature bydecomposition. The homogeneous catalyst can include active speciesselected from transition metals, alkali metals, and alkali earth metals.Ligands can be attached to the active species to improve the solubilityof the homogeneous catalyst in oil. The homogeneous catalyst can bedispersed a dispersal fluid to produce a catalyst feed.

The catalyst feed can be introduced at any point between flash drum 60and aqueous reforming unit 70 that can induce turbulence, such asrigorous mixing, of heavy fraction stream 162 containing the catalyst.Advantageously, adding the catalyst upstream of aqueous reforming unit70 can maximize dispersion of the catalyst particles in heavy fractionstream 162 and can reduce settling, or agglomeration, of catalyticparticles.

In at least one embodiment, the catalyst feed can be injected into theflash drum, as described with reference FIG. 4. Catalyst feed 166 can beinjected into flash drum 60. Catalyst feed 166 can include a catalystdispersed in a dispersal fluid. The dispersal fluid can includehydrocarbons having a viscosity less than 650 centistokes (cSt) at 122deg F. (50 deg C.), water, or a combination of hydrocarbons and water.The catalyst can be a heterogeneous catalyst or a homogeneous catalyst.The catalyst can be dispersed in the dispersal fluid according to knownmethods of mixing a solid and a liquid. In at least one embodiment, thecatalyst can be dispersed in the dispersal fluid using ultrasonic wavesfor at least two hours prior to injection as catalyst feed 166. Catalystfeed 166 can be injected directly into the flash drum, for example,through a port in flash drum 60. Alternately, catalyst feed 166 can bemixed with depressurized fluid 155 as shown in FIG. 4A and introducedinto the flash drum in that way. The catalyst is carried out of theflash drum in heavy stream 462 along with the heavy fractions and water.The flash drum 60 can include means for rigorous mixing. In at least oneembodiment, the integrated hydrothermal process can include means forinducing turbulence such that the induced turbulence increases mixingdownstream of flash drum 60. Catalyst feed 166 can be injected at aninjection rate that can maintain a weight ratio of catalyst tohydrocarbons in heavy stream 462 in the range of 0.05 to 0.07.

In at least one embodiment, the catalyst feed 166 can include a Ni (2 wt%)-Mg (5 wt %) supported on silicon dioxide catalyst. The Ni—Mg catalystcan be prepared by a conventional impregnation method using nickelnitrate and magnesium nitrate as precursors. The dried catalyst can becalcined at 450 deg C. for 6 hours under air before being used in theaqueous reforming unit 70. The silicon dioxide support can be fumedsilica having a particle size of 7 nanometers.

Returning to FIG. 2, the amount of water present in heavy fractionstream 162 is the desired amount of water for the upgrading reactions inaqueous reforming unit 70. The desired amount of water in aqueousreforming unit 70 can be between 1 wt % and 10 wt %, alternately between5 wt % and 10 wt %, and alternately between 5 wt % and 6 wt %. When theamount of water is less than 1 wt %, the steam reforming reactions inaqueous reforming unit 70 can be limited, reducing the extent ofupgrading. When the amount of water is higher than 10 wt %, hydrocarbonswill be too diluted by excessive steam, which can limit crackingreactions in the hydrocarbon oil phase. Steam in aqueous reforming unit70 can improve mass transfer of the reactant media. The boiling point ofthe hydrocarbons in aqueous reforming unit 70 is greater than thereaction temperature at the reaction pressure; therefore, the upgradingreactions in aqueous reforming unit 70 take place in the liquid phase.Light hydrocarbon gases, such as methane, ethane, and propane, can beproduced in aqueous reforming unit 70 and are kinetically stable at thereaction conditions and therefore, do not undergo additional reactions.In at least one embodiment, additional water can be added to aqueousreforming unit 70 (not shown) to achieve the desired amount of water inaqueous reforming unit 70. The additional water can be pressurized andheated to the operating conditions of aqueous reforming unit 70 prior tobeing introduced to aqueous reforming unit 70.

In at least one embodiment, aqueous reforming unit 70 can includeheating elements to increase the temperature of the internal fluid ascompared to the temperature of heavy fraction stream 162. The heatingelements can be external, such as heaters or heat exchangers. Heavyfraction stream 162 is introduced to aqueous reforming unit 70 in theabsence of a separation step to separate the oil and water in heavyfraction stream 162. In the absence of oil-water separation upstream ofaqueous reforming unit 70, aqueous reforming unit 70 can operate withoutthe addition of water. Advantageously, the heavy fraction stream can beintroduced to the aqueous reforming unit from the flash drum without theneed for further treatment or conditioning.

In an alternate embodiment, as shown in FIG. 5 and described withreference to FIG. 2, aqueous reforming outlet 170 can be mixed withlight fraction stream 160 in product mixer 66 to produce mixed fraction560. In this way, aqueous reforming outlet 170 can be separated into thecomponent, gas, liquid, and water phases in the same equipment thatseparates light fraction stream 160. This reduces the equipment costsand operating complexity of the process. Mixed fraction 560 can beintroduced to lights cooling device 65 to produce cooled mixed fraction565. Cooled mixed fraction 565 can be at a temperature greater than 50deg C. Cooled mixed fraction 565 can be introduced to lights separationzone 85 to produce gas phase product 580, petroleum phase product 590,and water phase stream 592. In an embodiment as shown in FIG. 5, wherethe catalyst has been introduced as a catalyst feed as shown withreference to FIG. 4, the separations in lights separation zone 85 can bedesigned such that water phase stream 592 includes at least 95% of thecatalyst from aqueous reforming unit 70, alternately at least 97% of thecatalyst from aqueous reforming unit 70, at least 98% of the catalystfrom aqueous reforming unit 70, and alternately at least 99% of thecatalyst from aqueous reforming unit 70. Petroleum phase product 590 andwater phase stream 592 can be treated to remove the catalyst by afiltering device (not shown). Gas phase product 580, petroleum phaseproduct 590, and water phase stream 592 can be treated as described withreference to gas product 180, petroleum product 190, and water product192 respectively.

According to an embodiment, as provided in FIG. 6 with reference to thedescription of FIG. 2, aqueous reforming outlet 170 can be introduced toreformer cooling device 72 to reduce the temperature of aqueousreforming outlet 170 to less than the boiling point of water for thegiven pressure. Reformer cooling device 72 can be any type of unitcapable of reducing steam to liquid water, such that cooled aqueousoutlet 670 contains liquid water. Cooled aqueous outlet 670 is in theabsence of steam. Cooled aqueous outlet 670 can be introduced toreformer pressure regulator 74 to produced reformed stream 672. Reformerpressure regulator 74 can be any pressure regulating device capable ofreducing the pressure of cooled aqueous outlet 670. In at least oneembodiment, reformer pressure regulator 74 can reduce the pressure ofcooled aqueous outlet 670 to atmospheric pressure. Reformed stream 672can be fed to reformer separation zone 75.

Reformer separation zone 75 can be a separation unit capable ofseparating a stream into its component gas phase, oil phase, and waterphase. Examples of separation zone 75 include a single three phaseseparator and a series of separation vessels. The series of separationvessels can include a vapor-liquid separator and an oil-water separator.Reformer separation zone 7 can separate reformed stream 672 intoreformed gas 678, reformed oil 676, and reformed water 674.

Reformed gas 678 can include hydrocarbons present as gases, such asmethane, ethane, ethylene, propane, propylene, i-butane, 1-butene,n-butene, i-pentane, carbon dioxide and hydrogen sulfide. Reformed gas678 can be released to atmosphere, further processed, or collected forstorage or disposal. Reformed water 674 can be recycled for use as waterstream 100, can be further processed, such as in a demineralizationprocess, to remove any impurities and then recycled for use as waterstream 100, or can be collected for storage or disposal. Reformed oil676 can have a lesser amount of the heavy fraction, reduced asphaltenecontent, reduced sulfur content, reduced nitrogen content, and reducedmetals content as compared to petroleum feed 115. Reformed oil 676 canhave a carbon residue (micro), determined from a micro carbon residuetest, less than the carbon residue of petroleum feed 115.

In embodiments where the catalyst has been introduced as a catalyst feedas shown with reference to FIG. 4, the separation of reformed stream 672can be designed such that reformed water 674 includes at least 95% ofthe catalyst from aqueous reforming unit 70, alternately at least 97% ofthe catalyst from aqueous reforming unit 70, at least 98% of thecatalyst from aqueous reforming unit 70, and alternately at least 99% ofthe catalyst from aqueous reforming unit 70. The remaining catalyst, thecatalyst not present in reformed water 674, is present in reformed oil676. Reformed water 674 and reformed oil 676 can be treated to removethe catalyst present by use of a filtering device (not shown).

In an alternate embodiment, as shown in FIG. 7 and described withreference to FIG. 2, petroleum product 190 can be fed to hydrogenationunit 95 to produce hydrogenated product 195. Petroleum product 190includes light hydrocarbons. Hydrogenation unit 95 can be anycommercially available process, including commercially availablehydrogenation catalyst.

In an alternate embodiment, as shown in FIG. 8 and described withreference to FIG. 2 and FIG. 3, slip stream 186 from gas product 180 canbe separated and fed to gas sweetening unit 82 to produce sweetened gasstream 185. Gas sweetening unit 82 can be any type of unit capable ofsweetening a gas phase stream. Examples of sweetening units can includethe use of an alkaline solution. Sweetened gas stream 185 can beintroduced to aqueous reforming unit 70. Removing hydrogen sulfide fromgas product 180 can prevent accumulation of sulfur in aqueous reformingunit 70. In at least one embodiment, sweetened gas stream 185 can bedissolved in a fluid and injected to reactor unit 40. The fluid caninclude water or oil.

In at least one embodiment, the process to upgrade heavy oil can includeboth a gas sweetening unit and a hydrogenation unit.

EXAMPLES Example 1

Example 1 is an Aspen-HYSYS simulation used to simulate the propertiesof light fraction stream 160 and heavy fraction stream 162 as shown inFIG. 9. Reactor effluent 140 was modeled to have a mass flow rate ofhydrocarbons of 100 kilograms per hour (kg/hr) and a mass flow rate ofwater of 100 kg/hr, for a total mass flow rate of 200 kg/hr. Thehydrocarbons in reactor effluent 140 were modeled to have an API gravityof 17.9 degrees. Reactor effluent 140 is depressurized from 3600 psig(24.8 MPa) to 260 psig (1.79 MPa) without a cooling device indepressurizing device 55 to produce depressurized fluid 155. Due toexpansion, the temperature of depressurized fluid 155 decreases to 361deg C. from 440 deg C., the temperature of reactor effluent 140.Depressurized fluid 155 is introduced to flash drum 60, which separatesdepressurized fluid 155 into light fraction stream 160 and heavyfraction stream 162. Table 1 provides the properties of the streams.

TABLE 1 Stream properties for Example 1. 140 160 162 Hydro- Hydro-Hydro- carbons Water carbons Water carbons Water Mass Flow 100.0 100.027.0 99.8 73.0 0.3 Rate (kg/h) API Gravity 17.9 — 22.9 — 16.0 —

As can be seen in Table 1, most of the water is carried in lightfraction stream 160, with the water content of heavy fraction stream 162being 0.27 wt %. The API gravity of hydrocarbons in light fractionstream 160 is higher than that of the hydrocarbons in heavy fractionstream 162. FIG. 10 shows the distillation curve for the hydrocarbons inreactor effluent 140 (hydrocarbons in reactor effluent), light fractionstream 160 (hydrocarbons in LFW), and heavy fraction stream 162(hydrocarbons in HFW). This example clearly shows that a supercriticalreactor unit can generate a good feed for a flash drum and aqueousreforming unit

Example 2

Example 2 illustrates the dependence of the composition of lightfraction stream 160 and heavy fraction stream 162 on the operatingconditions (temperature and pressure) of flash drum 60. An Aspen-HYSYSsimulation was used to simulate the properties of light fraction stream160 and heavy fraction stream 162 as shown in FIG. 9. Reactor effluent140 was modeled to have a mass flow rate of hydrocarbons of 100kilograms per hour (kg/hr) and a mass flow rate of water of 100 kg/hr,for a total mass flow rate of 200 kg/hr. The hydrocarbons in reactoreffluent 140 were modeled to have an API gravity of 17.9 degrees.Reactor effluent 140 is depressurized from 3600 psig (24.8 MPa) to 260psig (1.79 MPa) without a cooling device in depressurizing device 55 toproduce depressurized fluid 155. Due to expansion, the temperature ofdepressurized fluid 155 decreases to 361 deg C. from 440 deg C., thetemperature of reactor effluent 140. Flash drum 60 was modeled to have asource of heat, such that the temperature in flash drum 60 was increasedfrom 361 deg C. to 400 deg C. Depressurized fluid 155 is introduced toflash drum 60, which separates depressurized fluid 155 into lightfraction stream 160 and heavy fraction stream 162. Table 2 provides theproperties of the streams.

TABLE 2 Stream properties for Example 2. 140 160 162 Hydro- Hydro-Hydro- carbons Water carbons Water carbons Water Mass Flow 100.0 100.042.5 99.9 57.5 0.1 Rate (kg/h) API Gravity 17.9 — 21.6 — 15.1 —

Comparing Table 2 to Table 1 of Example 1 shows that the composition ofthe light fraction and heavy fraction, including the amount of water ineach stream depends on the operating conditions in flash drum 60. Byincreasing the temperature of flash drum 60, as in Example 2, morehydrocarbons can be separated in the light fraction, making the heavyfraction heavier than in Example 1.

Example 3

In Example 3, an Aspen-HYSYS process simulation was used to model theintegrated hydrothermal process, as shown in FIG. 11. Example 3 was asimulation based on experimental data. Petroleum feed 115 is simulatedas an atmospheric residue stream having an API gravity of 12.7 degree,the properties of which are in Table 3. Water stream 100 is simulated asdemineralized water having a conductivity less than 0.2 μS/cm². The flowrate of petroleum feed 115 was modeled as 50 L/hr. The flow rate ofwater stream 100 was modeled as 100 L/hr. The pressure of pressurizedwater 105 was at a pressure of 3600 psig (24.8 MPa). The pressure ofpressurized feed 120 was at a pressure of 3600 psig (24.8 MPa). Waterheater 10 increased the temperature of pressurized water 105 to atemperature of 500 deg C. Feed heater 20 increased the temperature ofpressurized feed 120 to a temperature of 120 deg C. Mixer 30 wassimulated as a simple tee mixer to mix heated water stream 110 andheated feed 135 to produce mixed fluid 130. Mixed fluid 130 is fed toreactor unit 40, which was at a temperature of 450 deg C. Reactoreffluent 140 was depressurized to 500 psig (3.45 MPa) in depressurizingdevice 55 to produce reduced fluid 955. In the simulation,depressurizing device 55 caused cooling of reactor effluent, such thatreduced fluid 955 was at a temperature less than the temperature ofreactor effluent 140. Reduced fluid 955 was fed to flash drum 60, whichis slightly heated to 360 deg C., to compensate for heat loss. Flashdrum 60 separated reduced fluid 955 into light fraction stream 160 andheavy fraction stream 162. Light fraction stream 160 is cooled in lightscooling device 65 to a temperature of 50 deg C. and then depressurizedin valve 67 to a pressure of 1 psig (6.89 kPa) to produce depressurizedlights fraction 1165. Depressurized lights fraction 1165 is thenseparated into gas phase 1180, oil phase 1190, and water phase 1192 inthree-phase separator 84. Heavy fraction stream 162 is fed to aqueousreforming unit 70. According to the stimulation, heavy fraction stream162 contains 0.55 weight percent water. Make-up water 1166, at apressure of 500 psig (3447 kPa) and temperature of 360 deg C., is fed toaqueous reforming unit 70 to increase the water content to 4.8 weightpercent. Aqueous reforming unit 70 was operated at a temperature of 435deg C. and a liquid hourly space velocity (LHSV) of 5.3/hr. Thesimulation included a catalyst of 2 wt % Ni-5 wt % Mg supported on asilicon dioxide composed of fumed silica particles having particle sizeof 7 nanometers (nm). The catalyst was mixed with make-up water 1166 ata ratio of catalyst to water of 2.5 to 100 by weight. The aqueousreforming unit 70 was exposed to ultrasonic waves for at least two hoursto disperse the catalyst. The catalyst injection rate was adjusted tomaintain a weight ratio of hydrocarbon to catalyst in the range between0.05 and 0.07 by weight. Aqueous reforming outlet 170 is cooled to atemperature of 50 deg C. in reformer cooling device 72 and depressurizedto a pressure of 1 psig in reformer pressure regulator 74 to producereformed stream 672. Reformed stream 672 is then separated in reformerseparation zone 75 into reformed gas 678, reformed oil 676, and reformedwater 674. The separation is made so that the catalyst is primarily inreformed water 674, with less than 1 weight % catalyst in reformed oil676. Used catalyst can be separated from reformed water 674 or reformedoil 676 by the use of a filtering unit (not shown). Reformed gas 678 ismixed with gas phase 1180 to produce gas stream 1178. Reformed oil 676is mixed with oil phase 1190 to produce oil stream 1176. Reformed water674 is mixed with water phase 1192 to produce separated water 1174.

TABLE 3 Properties of Feed and Product Streams Petroleum Oil streamProperties Feed 115 1176 Mass Flow (kg/hour) 49.0 46.2 Specific Gravity(Degree) 12.7 23.2  5% 362 258 10% 390 301 30% 468 378 Distillation(TBP) 50% 524 420 70% 588 468 90% 653 541 95% 673 571 Total SulfurContent (wt %) 4.0 3.4 Viscosity (cSt) at 50 deg C. 640 27 Asphalthene(Heptane-Insoluble) 4.8 0.3 Metals (V and Ni) (wtppm) 83 4

Tables 4 and 5 provide details of the mass balance and gas compositionsof various streams in the system.

TABLE 4 Mass Balance 115 100 1166 1178 1176 1174 Mass Flow (kg/hr) 49.099.8 1.5 3.1 46.2 101.0

TABLE 5 Composition of Gas in Gas Stream 926 Gas Component H₂O H₂S H₂ COCO₂ C₁ C₂ C₃ C₄ Wt % 9.1% 11.1% 5.5% 8.4% 10.7% 16.7% 14.0% 13.1% 11.3%

TABLE 6 Properties of Feed and Product Streams Petroleum ReactorProperties Feed 115 Effluent 140* Mass Flow (kg/hour) 49.0 48.1**Specific Gravity (Degree) 12.7 19.8  5% 362 297 10% 390 337 30% 468 420Distillation (TBP) 50% 524 464 70% 588 519 90% 653 592 95% 673 632 TotalSulfur Content (wt %) 4.0 3.7 Viscosity (cSt) at 50 deg C. 640 89Asphalthene (Heptane-Insoluble) 4.8 1.7 Metals (V and Ni) (wtppm) 83 0.2*Properties here are for the liquid hydrocarbons (hydrocarbons with morethan 4 carbons) in reactor effluent 140. **Represents the mass flow ofthe liquid hydrocarbons, the remaining mass flow is gas.

The results in Tables 3 and 6 show that the product from the integratedhydrothermal process is lighter than the feedstock. The liquid yieldfrom the process was 94 wt % suggesting that 6 wt % of the feed goesinto the gas-phase and water phase product.

Although the present embodiments have been described in detail, itshould be understood that various changes, substitutions, andalterations can be made hereupon without departing from the principleand scope. Accordingly, the scope of the embodiments should bedetermined by the following claims and their appropriate legalequivalents.

There various elements described can be used in combination with allother elements described here unless otherwise indicated.

The singular forms “a”, “an” and “the” include plural referents, unlessthe context clearly dictates otherwise.

Optional or optionally means that the subsequently described event orcircumstances may or may not occur. The description includes instanceswhere the event or circumstance occurs and instances where it does notoccur.

Ranges may be expressed here as from about one particular value and toabout another particular value or to about another particular value.When such a range is expressed, it is to be understood that anotherembodiment is from the one particular value to the other particularvalue, along with all combinations within said range.

Throughout this application, where patents or publications arereferenced, the disclosures of these references in their entireties areintended to be incorporated by reference into this application, in orderto more fully describe the state of the art, except when thesereferences contradict the statements made here.

As used throughout this application and in the appended claims, thewords “comprise,” “has,” and “include” and all grammatical variationsare each intended to have an open, non-limiting meaning that does notexclude additional elements or steps.

As used here, terms such as “first” and “second” are arbitrarilyassigned and are merely intended to differentiate between two or morecomponents of an apparatus. It is to be understood that the words“first” and “second” serve no other purpose and are not part of the nameor description of the component, nor do they necessarily define arelative location or position of the component. Furthermore, it is to beunderstood that that the mere use of the term “first” and “second” doesnot require that there be any “third” component, although thatpossibility is contemplated under the scope of the embodiments.

That which is claimed is:
 1. An integrated hydrothermal process forupgrading heavy oil, the integrated hydrothermal process comprising thesteps of: mixing a heated water stream and a heated feed in a mixer toproduce a mixed fluid, wherein the heated water stream is supercriticalwater, wherein the heated feed is at a feedstock temperature less than300 deg C. and a feedstock pressure greater than the critical pressureof water; introducing the mixed stream to a reactor unit to produce areactor effluent; allowing conversion reactions to occur in the reactorunit, wherein the reactor unit is maintained at a temperature greaterthan the critical temperature of water and at a pressure greater thanthe critical pressure of water, wherein the conversion reactions areoperable to upgrade the hydrocarbons in the mixed fluid such that thereactor effluent comprises light fractions, heavy fractions, and water;cooling the reactor effluent in a cooling device to produce a cooledfluid, where the cooled fluid is at a temperature less than the criticaltemperature of water and less than the temperature of the reactoreffluent; depressurizing the cooled fluid in a depressurizing device toproduce a depressurized fluid, where the depressurized fluid is at apressure less than the steam pressure corresponding to the temperatureof the cooled fluid such that water in the depressurized fluid ispresent as steam; mixing a catalyst feed with the depressurized fluid,wherein the catalyst feed comprises a catalyst, such that the catalystis dispersed in the depressurized fluid, such that the weight ratio ofhydrocarbons to catalyst in a heavy stream is in the range between 0.05and 0.07; introducing the depressurized fluid to a flash drum;separating the depressurized fluid in the flash drum to produce a lightfraction stream and a heavy fraction stream, wherein the light fractionstream comprises the light fractions and water, wherein the heavyfraction stream comprises the heavy fractions and water, wherein theheavy fraction stream comprises a water content between 0.1 wt % and 10wt %, such that the catalyst mixes with the heavy fraction to producethe heavy stream; introducing the heavy stream to an aqueous reformingunit; and allowing upgrading reactions to occur in the aqueous reformingunit to produce an aqueous reforming outlet, wherein the catalyst isoperable to catalyze the upgrading reactions in the aqueous reformingunit in presence of steam, wherein the aqueous reforming outletcomprises a greater concentration of light fraction relative to theheated feed.
 2. The integrated hydrothermal process of claim 1, furthercomprising the steps of: reducing the temperature of the light fractionstream in a lights cooling device to produce a cooled light fraction,wherein the cooled light fraction is at a temperature of 50 deg C.;introducing the cooled light fraction to a lights separation zone; andseparating the cooled light fraction in the lights separation zone toproduce a gas product, a petroleum product, and a water product.
 3. Theintegrated hydrothermal process of claim 2, further comprising the stepof: introducing the petroleum product to a hydrogenation unit to producea hydrogenated product.
 4. The integrated hydrothermal process of claim2, further comprising the steps of: separating a slip stream from thegas product; introducing the slip stream to a gas sweetening unit;removing an amount of hydrogen sulfide from the slip stream to produce asweetened gas stream; and introducing the sweetened gas stream to theaqueous reforming unit.
 5. The integrated hydrothermal process of claim1, further comprising the steps of: mixing the aqueous reforming outletand the light fraction stream in a product mixer to produce a mixedfraction; reducing the temperature of the mixed fraction in a lightscooling device to produce a cooled mixed fraction, wherein the cooledmixed fraction is at a temperature of 50 deg C.; introducing the cooledmixed fraction to a lights separation zone; and separating the cooledmixed fraction in the lights separation zone to produce a gas phaseproduct, a petroleum phase product, and a water phase stream.
 6. Theintegrated hydrothermal process of claim 1, further comprises the stepsof: increasing a pressure of a petroleum feed in a feed pump to producea pressurized feed, wherein a pressure of the pressurized feed isgreater than the critical pressure of water; increasing a temperature ofthe pressurized feed in a feed heater to produce the heated feed,wherein the heated feed is at the feedstock temperature; increasing apressure of a water stream in a water pump to create a pressurizedwater, wherein a pressure of the pressurized water is greater than thecritical pressure of water; and increasing a temperature of thepressurized water in a water heater to produce the heated water stream.7. The integrated hydrothermal process of claim 6, wherein the petroleumfeed is selected from the group consisting of whole range crude oil,reduced crude oil, atmospheric distillates, atmospheric residue streams,vacuum distillates, vacuum residue streams, cracked product streams,decanted oil, C10+ oil, liquefied coal, and biomaterial-derivedhydrocarbons.
 8. The integrated hydrothermal process of claim 1, whereinthe catalyst is selected from the group consisting of a homogeneouscatalyst and a heterogeneous catalyst.
 9. The integrated hydrothermalprocess of claim 8, wherein the catalyst is a heterogeneous catalystthat comprises an active species, a promoter, and a support material.10. The integrated hydrothermal process of claim 9, wherein theheterogeneous catalyst is a 2 wt % Ni-5 wt % Mg catalyst supported onsilicon dioxide.
 11. The integrated hydrothermal process of claim 8,wherein the catalyst is a homogeneous catalyst that comprises an activespecies and a ligand.
 12. The integrated hydrothermal process of claim6, wherein a ratio of a volumetric flow rate of the water stream to avolumetric flow rate of the petroleum feed at standard ambienttemperature and pressure is between 1:10 and 10:1.
 13. An integratedhydrothermal system for upgrading heavy oil, the integrated hydrothermalsystem comprising: a mixer, the mixer configured to mix a heated waterstream and a heated feed to produce a mixed fluid, wherein the heatedwater stream is supercritical water, wherein the heated feed is at afeedstock temperature less than 300 deg C. and a pressure greater thanthe critical pressure of water; a reactor unit fluidly connected to themixer, the reactor unit configured to maintain a temperature greaterthan the critical temperature of water, and further configured tomaintain a pressure greater than the critical pressure of water suchthat conversion reactions occur in the reactor unit, the conversionreactions are operable to upgrade the hydrocarbons in the mixed fluidsuch that a reactor effluent comprises light fractions, heavy fractions,and water; a cooling device fluidly connected to the reactor unit, thecooling device configured to reduce the temperature of the reactoreffluent to produce a cooled fluid, wherein the cooled fluid is at atemperature less than the critical temperature of water and less thanthe temperature of the reactor effluent; a depressurizing device fluidlyconnected to the cooling device, the depressurizing device configured toreduce the pressure of the cooled fluid to produce a depressurizedfluid, where the depressurized fluid is at a pressure less than thesteam pressure corresponding to the temperature of the cooled fluid suchthat water in the depressurized fluid is present as steam; a catalystmixer fluidly connected to the depressurizing device, the mixerconfigured to mix a catalyst feed and the depressurized fluid, whereinthe catalyst feed comprises a catalyst such that the catalyst isdispersed in the depressurized fluid at a weight ratio of catalyst tohydrocarbons in a heavy stream in the range of 0.05 to 0.07; a flashdrum fluidly connected to the catalyst mixer, the flash drum configuredto separate the depressurized fluid into a light fraction stream and aheavy fraction stream, wherein the light fraction stream comprises thelight fractions and water, wherein the heavy fraction stream comprisesthe heavy fractions and water, wherein the heavy fraction streamcomprises a water content between 0.1 wt % and 10 wt %; and an aqueousreforming unit fluidly connected to the flash drum, the aqueousreforming unit configured to upgrade the heavy fraction stream toproduce an aqueous reforming outlet, wherein the aqueous reforming unitcomprises a catalyst, wherein the catalyst is operable to catalyzeupgrading reactions in the presence of steam, wherein the aqueousreforming outlet comprises a greater concentration of light distillatesrelative to the petroleum feed.
 14. The integrated hydrothermal systemof claim 13, further comprising: a lights cooling device fluidlyconnected to the flash drum, the lights cooling device configured toreduce the temperature of the light fraction stream to produce a cooledlight fraction, wherein the cooled light fraction is at a temperature of50 deg C.; a lights separation zone, the lights separation zoneconfigured to separate the cooled light fraction into a gas product, apetroleum product, and a water product.
 15. The integrated hydrothermalsystem of claim 14, further comprising: a hydrogenation unit fluidlyconnected to the lights separation zone, the hydrogenation unitconfigured to produce a hydrogenated product, wherein the hydrogenatedproduct comprises.
 16. The integrated hydrothermal system of claim 14,further comprising: a gas sweetening unit fluidly connected to thelights separation zone, the gas sweetening unit configured to remove aportion of hydrogen sulfide from a slip stream of the gas product toproduce a sweetened gas stream.
 17. The integrated hydrothermal systemof claim 13, further comprising: a product mixer fluidly connected tothe aqueous reforming unit, the product mixer configured to mix theaqueous reforming outlet and the light fraction stream to produce amixed fraction; a lights cooling device fluidly connected to the productmixer, the lights cooling device configured to reduce the temperature ofthe mixed fraction to produce a cooled mixed fraction, wherein thecooled mixed fraction is at a temperature of 50 deg C.; a gas-liquidseparator fluidly connected to the lights cooling device, the gas-liquidseparator configured to separate the cooled mixed fraction into a gasphase product and a liquid phase product; and an oil-water separatorfluidly connected to the gas-liquid separator, the oil-water separatorconfigured to produce a petroleum phase product and a water phasestream.
 18. The integrated hydrothermal system of claim 13, wherein thecatalyst is selected from the group consisting of a homogeneous catalystand a heterogeneous catalyst.
 19. The integrated hydrothermal system ofclaim 18, wherein the catalyst is a heterogeneous catalyst thatcomprises an active species, a promoter, and a support material.